Textile treating compounds compositions and processes for treating textiles

ABSTRACT

NOVEL SOFTENING COMPOUNDS HAVING ONE LONG ALKYL GROUP CONTAINING 20 TO 30 CARBON ATOMS, I.E., ZWITTERIONIC, TERTIARY PHOSPHINE OXIDE AND ANIONIC SULFONATE COMPOUNDS; NOVEL LIQUID AND SOLID DETERGENT SOFTENER COMPOSITIONS CONTAINING SAID NOVEL SOFTENING COMPOUNDS OR ETHOXYLATED ALCOHOL, ETHOXYLATED ALCOHOL SULFATE OR TERTIARY AMINE OXIDE COMPOUNDS HAVING AN ALKYL GROUP CONTAINING 20 TO 30 CARBON ATOMS, SAID COPOSITIONS ALSO CONTAINING EITHER A CONVENTIONAL ORGANIC DETERGENT, A BRIGHTENING AGENT, ALKALINE DETEGENCY BUILDER SALTS OR MIXTURES THEREOF; PROCESSES FOR THE SOFTENING OF TEXTILES DURING THE WASH OR RINSE CYCLE OF THE LAUNDERING PROCESS EMPLOYING CRITICAL AMOUNTS OF SAID SOFTENING COMPOUNDS.

United States Patent Oihce 3,649,569 TEXTILE TREATING COMPOUNDS,COMPOSI- TIONS AND PROCESSES FOR TREATING TEXTILES Charles BruceMcCarty, Cincinnati, Ohio, assignor to The Procter & Gamble Company,Cincinnati, Ohio No Drawing. Continuation-impart of application Ser. No.648,527, June 5, 1967. This application May 29, 1969, Ser. No. 829,093

Int. Cl. D06m 13/30 U.S. Cl. 252-543 17 Claims ABSTRACT OF THEDISCLOSURE Novel softening compounds having one long alkyl groupcontaining 20 to 30 carbon atoms, i.e., zwitterionic, tertiary phosphineoxide and anionic sulfonate compounds; novel liquid and solid detergentsoftener compositions containing said novel softening compounds orethoxylated alcohol, ethoxylated alcohol sulfate or tertiary amine oxidecompounds having an alkyl group containing 20 to 30 carbon atoms. saidcompositions also containing either a conventional organic detergent, abrightening agent, alkaline detergency builder salts or mixturesthereof; processes for the softening of textiles during the wash orrinse cycle of the laundering process employing critical amounts of saidsoftening compounds.

This application is a continuation-in-part of my copending application,Ser. No. 648,527, filed June 5, 1967 and now abandoned for TextileTreating Compounds, Composition and Processes for Treating Textiles.

BACKGROUND OF THE INVENTION (1) Field of invention This inventionrelates to novel softening compounds, detergent compositions containingthese novel softening compounds, and processes for softening textilematerials. Hereinafter the terms softening agents and softeningcompounds are used interchangeably.

The use of softening agents to improve the softness or hand of textilematerials is well-known. Aside from imparting softness to textiles,softening agents generally prevent the accumulation of static electriccharges and make the ironing of the textile easier. Only in the pastdecade have softening agents become generally known to the housewife.Prior to this time soap residues provided the same effect of hand orsoftness. With the advent of synthetic detergents which effectivelyremove fatty residues from the textile material this benefitdisappeared. Obviously, if fatty materials were to be added to thelaundering process to obtain softening, it would be necessary to addthem during the rinse cycle or in the drying cycle where no syntheticdetergent is present. However, such addition of fatty materials appearedimpractical as a comparatively large amount (about 1% of the fabricweight) is required to produce an appreciable softening effect.

In the light of these problems, cationic surface active agents having atleast one long alkyl radical, usually containing about 18 carbon atoms,were developed. They have proved to be effective softeners and can beused at very low concentrations in the rinse water, i.e., about 0.05%based on the weight of the textile. Most of the softeners used in homelaundry situations today are cationics. Despite the effectiveness ofthese cationic softening agents, they do have certain drawbacks. Forexample, they are not compatible with anionic detergents which are usedin most heavy-duty detergent compositions. When the cationic softeningagent is used in the 3,649,569 Patented Mar. 14, 1972 presence ofanionic detergents, a scum is formed due to the reaction between thecationic softening agent and the anionic detergent. Even if the cationicsoftening agents are used with a nonionic detergent, the cationicsgenerally will not attach to the textile material during the launderingprocess in sufficient quantity to do much softening. Thus, the cationicsoftening agent must, to be elfective, be added separately in the rinsecycle. Almost all of the softeners used under domestic conditions are soadded, necessitating an extra step in the Washing process which forcesthe housewife to return to the washing machine during the rinse cycle.

Another problem associated with the use of cationic softeners is theireffect on the brightening effectiveness of brightener compounds used inconjunction with them. Because of yellowing associated with the use ofcationic softening agents and that yellowing discoloration whichinherently develops in cotton fabric on aging, it is desirable to add abrightening agent to softener formulations. Such brighteners counteractthe yellow hue of the fabric by giving off a blue-white fluorescence.Addition of brighteners to softener formulations intended for householduse is common and such formulations are greatly preferred by the averagehousewife. The best and most commonly used brighteners, however, arevery inefiicient When used in cationic formulations. The reasons forthis are not entirely understood, but the brightness conferred to cottonby a given amount of such a brightener when it is applied to the clothfrom a cationic softener solution is only one-quarter to one third asmuch as that brightness conferred to cotton by the same amount ofbrightener applied to the cloth from distilled water. Since thebrightener compounds are extremely expensive, a softener formulationwhich would permit more efficient brightener usage would be highlydesirable.

(2) Description of prior art The lower homologs of the softeningcompounds which have been found to be useful in the present inventionare well known as synthetic detergent compounds. The following patentsdisclose the lower homologs of the softening agents of this invention:DAS 1,162,966, Canadian 706,408, U.S. 3,227,749, U.S. 3,047,579, British995,260, U.S. 3,178,370, U.S. 2,930,760 and U.S. 1,970,578. There isnothing in the art which indicates that the higher homologs of thesedetergent compounds would have softening characteristics.

SUMMARY This invention provides a novel class of softening agents whichcontain substituents containing from 20 to 30 carbon atoms. The novelC2040 substituent-containing softening agents of this invention comprisethe following subclasses:

(1) Novel zwitteriom'c compounds having the formula wherein R and R areselected from the group consisting of ethyl, methyl, n-propyl,isopropyl, 2-hydroxyethyl and 2-hydroxypropyl, R is a carbon chaincontaining 20 to 30 carbon atoms selected from the group consisting ofalkly and alkenyl groups and wherein said alkyl and alkenyl groupscontain from O2 hydroxyl substituents, from 0-5 ether linkages and 0-1amide linkage, and R is an alkylene group containing from 1 to 4 carbonatoms with 0-1 hydroxyl substituents;

(2) Novel tertiary phosphine oxide compounds having the formula R R R PO wherein R is selected from the group consisting of alkyl, alkenly andmonohydroxy alkyl groups having a chain length from 20 to 30 carbonatoms, and wherein R and R are each selected from a group consisting ofalkyl and monohydroxy alkyl groups containing from 1 to 4 carbon atoms;and

(3) Novel anionic sulfonate compounds having the formula wherein M isselected from a group consisting of alkali metal, ammonium andsubstituted ammonium cations, and R is an alkyl group containing from 20to 30 carbon atoms.

Also provided are the following compositions:

(a) Compositions comprising from about 1% to about 20% of a conventionalwater-soluble synthetic organic detergent having one long alkyl groupcontaining less than 20 carbon atoms and from about 1% to about 25% ofthe novel softening agents of the invention or the ethoxylated alcohol,ethoxylated alcohol sulfate, or amine oxide softening agents describedhereinafter;

(b) Compositions comprising from 1% to about 25 of the novel softeningagents of the invention or the ethoxylated alcohol, ethoxylated alcoholsulfate, or amine oxide softening agents described hereinafter as thesole detergent and from about 1% to about 90% of a watersoluble alkalinedetergency builder salts; and

(c) Compositions comprising from 1% to about 25 of the novel softeningagents of the invention or the ethoxylated alcohol, ethoxylated alcoholsulfate, or amine oxide softening agents described hereinafter, fromabout .01% to about 1% of brightener com-pounds and the balance water.This invention also provides processes for treating textile using, e.g.,the above compositions and/or novel softening agents.

It has been discovered that the compounds of the present invention whichare employed in the processes and compositions embodied in the inventionhave outstanding softening characteristics and are as effective as themost often used cationic softeners. The softening compounds of thisinvention neither interact with anionic detergents not affect thebrightening effectiveness of the best and most often used brighteningagents as do cationic softening agents. Aside from their softeningeffectiveness, the softening compounds of this invention exhibitdetergency characteristics. Thus, the compounds of this invention can beadvantageously used in conjunction with detergents and brighteningagents.

(A) NOVEL SOFTENING COMPOUNDS OF THE INVENTION The novel compounds ofthe invention are characterized as follows:

(1) Zwitterionic compounds having the formula wherein R and R are eachselected from the group consisting of methyl, ethyl, n-propyl,isopropyl, 2-hydroxyethyl and 2-hydroxypropyl, R is a carbon chaincontaining from 20 to 30 carbon atoms selected from the group consistingof alkyl and alkenyl groups and wherein said alkyl and alkenyl groupscontain from 0-2 hydroxyl substituents, from 0-5 ether linkages, and 0-1amide linkage and R is an alkylene group containing from 1 to 4 carbonatoms with 0 to 1 hydroxyl substituents.

(a) Preferred zwitterionic compounds The preferred compounds of thisclass of softening agents are generically described as follows:

wherein R and R are each selected from the group con sisting of methyl,ethyl, n-propyl, isopropyl, Z-hydroxyethyl and Z-hydroxypropyl groups, Ris a carbon chain containing from 20 to 26 carbon atoms selected fromthe group consisting of alkyl and alkenyl groups and Wherein said alkyland alkenyl groups contain 02 hydroxyl substituents, and R is analkylene group containing 1 to 4 carbon atoms with 0-l hydroxylsubstituent.

Specific examples of the most preferred compounds of this class are asfollows:

3 (N-eicosyl-N,N-dimethy1ammonio)-2-hydroxypropanel-sulfonate3-(N-eicosyl-N,N-dimethylammonio)-propane-1- sulfonate 3-[N-eicosyl-N,N-di( Z-hydroxyethyl ammonio -2-hydroxypropanel-sulfonate 3N-doco syl-N,N-dimethylammonio -2-hydroxypropane-1 -sulfonate 3-(N-docosyl-N,N-dimethylammonio -propane-lsulfonate 3-[N-docosyl-N,N-bis-(2-hydroxyethyl) ammonio] Z-hydroxypropane- 1 -sulfonate3-(N-tetracosyl-N,N-dimethylammonio -2-hydroxypropanel-sulfonate 3-(N-tetracosyl-N,N-dimethylammonio) -propanel-sulfonate 3N-tetracosyl-N,N-bis-( Z-hydroxyethyl ammonio]Z-hydroxypropanel-sulfonate 3-( N-hexacosyl-N,N-dimethylammonio)-2-hydroxypropane-l-sulfonate 3-(N-hexacosyl-N,N-dimethylammonio)-propane-lsulfonate Examples of other preferred compounds of this classare as follows:

3 N-eicosyl-N- ethyl-N-methylammonio -2-hydroxypropane-l-sulfonate 3-(N-docosyl-N-ethyl-N-methylammonio) -2-hydroxypropane-l-sulfonate3-(N-docosyl-N,N-diethylammonio) -propane-lsulfonate3-(N-tetracosyl-N-ethyl-N-methylammonio)-2-hydroxypropane-l-sulfonate(b) Other zwitterionic compounds Examples of other compounds within thisclass which are useful as softening agents are as follows:

3- [N- 2-steramidoethyl) -N-propyl-N-isopropy1] butane-sulfonate 3- [N-3,5 -dioxatetracosy1) -N,N-dimethylammonio] 2-hydroxyprop anel-sulfonate[N- 3-docosenyl -N- Z-hydroxypropyl -N-methylammonio]pentane-1-sulfonate 6- N- 2-hydroxydocos-4-enyl -N,N-dimethylammonio]hexanel-sulfonate 5 [N- 4-steramidob ut-Z-enyl -N,N-diethylammonio] -2-hydroxypentanel-sulfonate 4- N- 3 ,5 -dioxahexacos- 1 O-enyl-N,N-dimethylammonio 1 -3-hydroxybutanel-sulfonate The synthesis of thelower homologs of the novel softening compounds of this class is wellknown. See DAS 1,018,421 (Boehme Fettchemie G.m.b.H., Aug. 24. 1961) andShell Bulletin -IT-47-l1/ 60. To simply illustrate such syntheses asapplied to the compounds of this invention, consider the synthesis oftwo of the members of this class: (a) 3-(N-eicosyl-N,N-dimethylammonio)2 hydroxypropane-l-sulfonate and (b)3-(N-eicosyl-N,N-dimethylammonio)-propane 1 sulfonate. To form compound(a) the reaction product prepared by reacting epichlorohydrin withsodium bisulfite is reacted in turn with a tertiary amine having thefollowing structure:

Hz This type of quaternization reaction is described in Ralston, A. W.,Fatty Acids and Their Derivatives, pp. 684- 696 (1948). To form compound(b) the simplest synthesis is, generally, as follows: a tertiary aminehaving the following structure i C2OH-H III is reacted with propanesultone.

(2) Tertiary phosphine oxide compounds having the formula R R R P- Owherein R is selected from the group consisting of alkyl, alkenyl andmonohydroxy alkyl groups having a chain length of from to carbon atoms,and wherein R and R are each selected from the group consisting of alkyland monohydroxy alkyl groups containing from 1 to 4 carbon atoms.

(a) Preferred tertiary phosphine oxide compounds Preferred compounds ofthis class are generically described as having the formula R R R P Owherein R is selected from the group consisting of alkyl, alkenyl andmonohydroxy alkyl groups having a chain length of from 20 to 26 carbonatoms, and wherein R and R are each selected from a group consisting ofmethyl, ethyl and ethanol.

Specific examples of the most preferred compounds of this class are asfollows:

Eicosyldimethylphosphine oxide Eicosyldi(2-hydroxyethyl)phosphine oxideDocosyldimethylphosphine oxide Docosyldi(2-hydroxyethyl)phosphine oxideTetracosyldimethylphosphine oxide Hexacosyldimethylphosphine oxideEicosyldiethylphosphine oxide Docosyldiethylphosphine oxideTetracosyldi(Z-hydroxyethyl)phosphine oxide Other examples of thepreferred compounds of this class are as follows:

Eicosylmethylethylphosphine oxide Heneicosyldimethylphosphine oxidefi-Hydroxyeicosyldimethylphosphine oxidefi-Hydroxydocosyldimethylphosphine oxide Heneicosylmethylethylphosphineoxide Heneicosyldi (2-hydroxyethyl)phosphine oxideDocosylmethylethylphosphine oxide Tricosyldimethylphosphine oxideTricosylmethylethylphosphine oxide Tetracosylmethylethylphosphine oxideTetracosyldi Z-hydroxyethyl) phosphine oxide Pentacosyldimethylphosphineoxide Hexacosyldi(2-hydroxyethyl)phosphine oxide (b) Other tertiaryphosphine oxide compounds Other compounds of this class are as follows:

Eicosylmethyl-Z-hydroxybutylphosphine oxide Eicosyldibutylphosphineoxide Eicosylmethyl-2-hydroxypropylphosphine oxideDocosylmethyl-2-hydroxypropylphosphine oxideDocosylmethyl-3-hydroxybutylphosphine oxide2-tetracosenylmethylethylphosphine oxide Heptacosyldimethylphosphineoxide Heptacosyldiethylphosphine oxide Octacosyldimethylphosphine oxideOctacosyldiethylphosphine oxides Nonacosyldimethylphosphine oxideNonacosyldiethylphosphine oxide Triacontyldimethylphosphine oxideTriacontyldiethylphosphine oxide The lower homolog tertiary phosphineoxide of this class are prepared by methods such as those discussed byK. Darrell Berlin and G. B. Butler, Chemical Review, vol. 60, pp.243-259, June 1960. Using similar synthesis the tertiary phosphineoxides of this invention can be prepared by oxidizing the correspondingphosphine with, for example, hydrogen peroxide.

3. Anionic sulfonate compounds having the formula In m o o H -S 0 M Hwherein M is selected from a group consisting of alkali metal, andsubstituted ammonium cations, and R is an alkyl group containing from 20to 30 carbon atoms.

(a) Preferred anionic sulfonate compound Examples of preferred softeningcompounds of this class are anionic sulfonate compounds having thestructural formula above wherein R is an alkyl group containing 20 to 26carbon atoms, such as: sodium and potassium 2-acetoxydocosylsulfonate,ammonium 2-acetoxydocosylsulfonate, diethanolarnmonium 2acetoxydocosylsulfonate, sodium and potassium2-acetoxytricosylsulfonate, sodium and potassium2-acetoxytetracosylsulfonate, sodium and potassium Z-acetoxypentacosylsulfonate, sodium and potassium 2-acetoxyhexacosylsulfonate, sodium andpotassium 2-acetoxyheptacosylsulfonate, and sodium and potassium2-acetoxyoctacosylsulfonate.

(b) Other anionic sulfonate compounds Other suitable compounds of thisclass include sodium and potassium 2-acetoxynonacosylsulfonate, sodiumand potassium Z-acetoxytriacontylsulfonate, sodium and potassium2-acetoxyheneitriacontylsulfonate and sodium and potassium2-acetoxydotriacontylsulfonate. I

The following synthesis of the simplest compound of this class, sodium2-acetoxydocosylsulfonate, is illustrative of the method by which thesoftening compounds of this class can be produced: Sodium2-hydroxydocosylsulfonate (0.364 mole) is placed in a one-literthreenecked standard taper flask equipped with stirrer and condenser. Apremixed solution of pyridine (1.36 moles) and acetic anhydride (7.35moles) is added to this flask. The mixture is then heated on a steambath for one week. Then, the mixture is evaporated to dryness and thesolids dissolved in 1500 ml. of nearly boiling dioxane, treated withactivated charcoal and filtered while hot. The product is thenrecrystallized from one liter of dioxane to produce 94.9% sodium2-acetoxydocosylsulfonate.

7 (B) KNOWN COMPOUNDS USED AS SOFTENING COMPOUNDS IN THE INVENTION (1)It has been discovered that certain known tertiary amine oxide compoundsare useful as softening agents in the compositions and processesembodied in the present invention. Such tertiary amine oxide compoundshave the formula R R R N O wherein R is a straight or branched carbonchain containing from 20 to 30 carbon atoms selected from the groupconsisting of alkyl and alkenyl groups and wherein said alkyl andalkenyl groups contain from -2 hydroxyl substituents, from 0-5 etherlinkages there being at least one moiety of at least 20 carbon atomscontaining no ether linkages, and 0-4 amide linkage, and wherein R and Rare each selected from the group consisting of alkyl and monohydroxyalkyl groups containing from 1 to 4 carbon atoms and wherein R and R canbe joined to form a heterocyclic group containing from 4 to 6- atoms.

(a) Preferred tertiary amine oxide compounds Preferred compounds of thisclass are generically described having the formula R R R N O wherein Ris a straight or branched carbon chain containing to 26 carbon atomsselected from the group consisting of alkyl, alkenyl and monohydroxyalkyl groups and wherein R and R are each selected from a groupconsisting of methyl, ethyl and ethanol.

Specific examples of the softening compounds of this class which arepreferably employed, alone or in combination, in the compositions andprocesses of this invention are as follows:

Eicosyl-bis- (fi-hydroxyethyl amine oxide Eicosyldimethyiamine oxideDocosyldimethylamine oxide Docosyl-bis-(fl-hydroxyethyl)amine oxideTetracosyldimethylamine oxide T etracosyl-bis-( ,B-hydroxyethyDamineoxide Hexacosyldimethylamine oxide Hexacosyl-bis-(fi-hydroxyethynamineoxide Examples of other preferred softening compounds of this class areas follows:

2-hydroxyeicosyldimethylamine oxide Eicosylmethylethylamine oxideEicosyldiethylamine oxide 2-eicosyldiethylamine oxideHeneicosyldimethylamine oxide Heneicosyldiethylamine oxideDocosylmethylethylamine oxide Docosyldiethylamine oxideTricosyldimethylamine oxide Tricosyldiethylamine oxideTetracosylmethylethylamine oxide 1I-tetracosyldimethylamine oxide Tetracosyldiethylamine oxide ,d-Hydroxytetracosyldimethylamine oxidePentacosyldimethylamine oxide Pentacosyldiethylamine oxideHexacosyldiethylamine oxide (b) Other tertiary amine oxide compoundsExamples of other amine oxide softening compounds which are useful inthe process of this invention, alone or in combination, are as follows:

Eicosylmethyl(Z-hydroxypropyl) amine oxide Eicosylmethylpropylamineoxide Docosylbutylrnethylamine oxide 2-docosenyldimethylamine oxide2-methoxydocosyldimethylamine oxide Heptacosyldimethylamine oxideHeptacosyldiethylamine oxide Octacosyldimethylamine oxideOctacosylmethylethylamine oxide Octacosyl-bis- (fi-hydroxyethyl amineoxide Octacosyldiethylamine oxide Nonacosyldiethylamine oxideNonacosyldimethylamine oxide Triacontyldimethylamine oxideTriacontyldiethylamine oxide 3,6-dioxaoctacosyldimethylamine oxide2-hydroxy-4-oxatetracosyldimethylamine oxide4-hydroxytetracos-2-enyldimethylamine oxide4,8triacont-2-enyldimethylamine oxide4-stearamido-2-butenyldimethylamine oxide N-eicosylmorpholine-N-oxideN-docosylmorpholine-N-oxide 6-stearamidohexyldimethylamine oxidefl-Behenamidoethyldimethylamine oxide Behenylglyceryl fl-hydroxyethyl)methylamine oxide N-docosylpyrrolidine-N-oxideN-eicosylpiperidine-N-oxide N-tetracosylpyridine-N-oxide The use of theforegoing tertiary amine oxide compounds as softening agents for thetreatment of textiles during the rinse cycle is covered in the copendingapplication of Warren 1. Lyness, entitled Softening of TextileMaterials, Ser. No. 643,343, filed June 5, 1967 and now Pat. No.3,554,784.

(2) Ethoxylated alcohol compounds having the formula R O(C H4O),,Hwherein x equals an integer of from 3 to 45 and R is an alkyl groupcontaining from 20 to 30 carbon atoms.

(a) Preferred ethoxylated alcohol compounds Examples of preferredsoftening compounds of this class are as follows: the condensationproduct of reacting from 3 moles to 45 moles of ethylene oxide (e.g., 3,9, 12, 15, 20 and 30 moles) with one mole of alcohol selected from thegroup consisting of eicosyl alcohol, heneicosyl alcohol, tricosylalcohol, tetracosyl alcohol, pentacosyl alcohol and hexacosyl alcohol.

The ethoxylated alcohol softening compounds of this class can begenerally prepared as follows: an alcohol containing 20 to 30 carbonatoms is mixed with NaOH, and ethylene oxide is bubbled into the mixtureat elevated temperatures [see Weimer and Cooper, Component Distributionof Alcohol, Ethylene Oxide Adclucts, 43 I.A.O.C.S., pp. 440-5 (July1966)].

(3) Ethoxylated alcohol sulfates having the formula R O(C H O) SO' Mwherein x equals an integer of from 1 to 20, M is selected from thegroup consisting of alkali metals, ammonium and substituted ammoniumcations, and R is an alkyl group containing from 20 to 30 carbon atoms.

(a) Preferred ethoxylated alcohol sulfate compounds Examples ofpreferred softening compounds of this class are as follows: The alkalimetal (e.g., sodium and potassium), ammonium and substituted ammoniumcation (e.g., monoethanol and diethanol ammonium) salts of the sulfatedcondensation product of from 1 to 20 moles of ethylene oxide (e.g., 1,3, 9, 12, 16 and 20 moles) with one mole of alcohol selected from thegroup consisting of eicosyl alcohol, heneicosyl alcohol, tricosylalcohol, tetracosyl alcohol, pentacosyl alcohol and hexacosyl alcohol.

(b) Other ethoxylated sulfate compounds Other suitable softeningcompounds of this class include the alkali metal (e.g., sodium andpotassium), ammonium, and substituted ammonium cations (e.g.,monoethanol and diethanol ammonium) salts of the sulfated condensationproduct of from 1 to 20 moles of ethylene oxide with one mole of alcoholselected from the group consisting of heptacosyl alcohol, octacosylalcohol, nonacosyl alcohol, and triacontyl alcohol.

The ethoxylated alcohol sulfates of this class can be prepared,generally, by reacting the ethoxylated alcohol compounds of (3) abovewith sulfuric acid and then neutralizing the product with an alkalimetal or substituted ammonium base (e.g., sodium, potassium, andammonium hydroxides or carbonates).

The limits defined above in delineating the carbon content in the longalkyl group of the softening compounds of this invention were determinedon the basis of economic, solubility and softening considerations.Compounds containing long alkyl groups of more than carbon atoms areusually too costly and too insoluble in water, while compoundscontaining alkyl groups of less than 20 carbon atoms are not effectivesofteners.

It was discovered that each of the foregoing classes of softeningcompounds were surprisingly more effective than their lower homologs,i.e., the C homologs. The reason for this unexpected increase insoftening effectiveness is not known and was unpredictable. Theunexpected softening effectiveness of the various novel compounds of thepresent invention are illustrated by Example 11 comparing the softeningeffectiveness of the novel compounds with the softening effectiveness oftheir lower homologs.

It was found that all of the foregoing softener compounds can beemployed, alone or in combination, in novel liquid and solid detergentcompositions. As pointed out above, the discovery that the softenercompounds of the present invention can be used in conjunction withheavy-duty anionic detergents to form detergent compositions withexcellent softening characteristics is particularly advantageous.

(C) COMPOSITIONS OF THE INVENTION The compositions of this inventioncomprise three embodiments as set forth in detail hereinafter. In thefirst embodiment, the composition comprises as essential ingredients aconventional water-soluble synthetic organic detergent and certainsoftening agents. In the second embodiment, the composition comprises asessential ingredients certain softening agents which also act as thesole detergent active and water-soluble alkaline detergency buildersalts. The third embodiment comprises as essential ingredients certainsoftening agents and brightener compounds.

(1) Compositions containing conventional organic synthetic detergent asan essential ingredient This embodiment of the present invention relatesto the novel combination of synthetic organic detergent compounds withthe foregoing softening agents forming liquid and granular detergentcompositions which exhibit effective softening properties. Thesedetergent compositions can, if desired, be built with variouswater-soluble alkaline builder salts.

More specifically, this embodiment of the present invention relates tocompositions consisting essentially of:

In the foregoing detergent compositions, whether liquid or granular, theamount of softening agent present is preferably from about 2.0% to 10%by weight and the amount of detergent present is preferably from about2% to about 18% by weight.

The softening agents of the present invention exhibit excellentdetergency characteristics and it has been found that formulationscontaining ratios of softener to synthetic organic detergent in therange of 4:1 to about 1:20 by 10 weight have good detergency andsoftening characteristics. However, formulations containing ratios ofsoftener to synthetic organic detergent in about a 1:1 ratio have beenfound to have preferred detergency and softening properties.

(2) Compositions containing detergency builder as an essentialingredient This embodiment of the present invention relates to the novelcombination of the softening agents of the present invention as the soledetergent active With watersoluble alkaline detergency builder salts.More specifically, this embodiment of the present invention relates tocompositions consisting essentially of (a) from about 1% to about 25%and more preferably from about 10% to about 20% of a softening agentselected from the group consisting of subclasses (1)- (3) of the novelsoftening agents described above in the Summary section, the previouslyknown compounds described above in Section B and mixtures thereof,

(b) from about 1% to about of a water-soluble alkaline detergencybuilder salt, and

(c) the balance being water, all percentages by weight.

(3) Liquid compositions containing brightner compound as an essentialingredient This embodiment of the present invention relates to the novelcombination of the softening agents of the invention with certainbrightener compounds in liquid softener formulations. More specifically,this embodiment of the present invention relates to compositionsconsisting essentially of (a) from about 1% to about 25 and morepreferably from about 1% to about 10% of a softening agent selected fromthe group consisting of (1)-(3) of the novel softening compoundsdescribed above in the Summary section, and the previously knowncompounds described in Section B and mixtures thereof,

(b) from about 0.01% to about 1% of a brightner compound and (c) thebalance being water, all percentages being by weight.

It has been discovered that the softening compounds of the presentinvention do not interfere with the brightening effectiveness of thebrighteners generally preferred for domestic laundering operations.These brighteners will be discussed further below. Generally,brightening agents are employed in the foregoing detergent and liquidsoftener formulations in the amount of 0.01% to 1.0% by weight and mostpreferably from 0.1% to 0.8% by weight of the total composition.

The softening compounds which are preferred for use in the detergentcompositions of this invention are those preferred compounds set out inSection A and Section B above. Softening agents (1)(3) are the mostpreferred compounds. The preferred softening agents for the compositionsof embodiment 3 are novel softening agents (2)-(3) and the knowncompounds of section B.

Water soluble synthetic organic detergents.Among the synthetic organicdetergents which can be employed in the foregoing detergent compositionsand are within the contemplation of this invention are as follows:

(a) Anionic synthetic detergents: This class of synthetic detergents canbe broadly described as the water-soluble salts, particularly the alkalimetal salts, of organic sulfuric reaction products having in theirmolecular structure an alkyl radical containing from about 8 to about 18carbon atoms, and a radical selected from the group consisting ofsulfonic acid and sulfuric acid ester radicals. (Included in the termalkyl is the alkyl portion of higher acyl radicals.) Important examplesof the synthetic dctergents which form a part of the preferredcompositions of the present invention are the sodium alkyl sulfates,especially those obtained by sulfating the higher alcohols (C -C carbonatoms) produced by reducing the glycerides of tallow or coconut oil;sodium or potassium alkylbenzenesulfonates, in which the alkyl groupcontains from about 9 to about carbon atoms, especially those of thetypes described in United States Letters Patent Nos. 2,220,099 and2,477,383; sodium alkylglyceryl ether sulfonates, especially thoseethers of the higher alcohols derived from tallow and coconut oil;sodium coconut oil fatty acid monoglyceride sulfates and sulfonates;sodium or potassium salts of sulfuric acid esters of the reactionproduct of one mole of a higher fatty alcohol (e.g., tallow or coconutoil alcohols) and about 1 to 6 moles of ethylene oxide; sodium orpotassium salts of alkylphenol ethylene oxide ether sulfates with about1 to about 10 units of ethylene oxide per molecule and in which thealkyl radicals contain about 9 to about 12 carbon atoms; the reactionproduct of fatty acids esterified with isethionic acid and neutralizedwith sodium hydroxide, Where, for example, the fatty acids are derivedfrom coconut oil; sodium or potassium salts of fatty acid amines of amethyltauride in which the fatty acids, for example, are derived fromcoconut oil; and others known in the art, a number being specificallyset forth in United States Letters Patent Nos. 2,486,921; 2,486,922 and2,396,278.

(b) Nonionic synthetic detergents: This class of synthetic detergentsmay be broadly defined as compounds, aliphatic or alkyl aromatic innature, which do not ionize in water solution.

For example, a well-known class of nonionic synthetic detergents is madeavailable on the market under the trade name of Pluronic. Thesecompounds are formed by condensing ethylene oxide with a hydrophobicbase formed by the condensation of propylene oxide with propyleneglycol. The hydrophobic portion of the molecule which, of course,exhibits water-insolubility has a molecular weight of from about 1200 to2500. The addition of polyoxyethylene radicals to this hydrophobicportion tends to increase the water-solubility of the molecule as awhole and the liquid character of the product is retained up to thepoint where polyoxyethylene content is about 50% of the total weight ofthe condensation product.

Other suitable nonionic synthetic detergents include:

(1) The polyethylene oxide condensates of alkylphenols, e.g., thecondensation products of alkylphenols or dialkylphenols wherein thealkyl groups contain from about 6 to 12 carbon atoms in either astraight chain or branched chain configuration, with ethylene oxide, thesaid ethylene oxide being present in amount equal to 10 to moles ofethylene oxide per mole of alkylphenol. The alkyl substituent in suchcompounds may be derived from polymerized propylene, diisobutylene,n-octene, or n-nonene, for example.

(2) Those derived from the condensation of ethylene oxide with theproduct resulting from the reaction of propylene oxide andethylenediarnine. For example, compounds containing from about to about80% polyoxyethylene by weight and having a molecular weight of fromabout 5000 to about 11,000 resulting from the reaction of ethylene oxidegroups with a hydrophobic base constituted of the reaction product ofethylenediamine and excess propylene oxide, said base having a molecularweight of the order of 2500 to 3000, are satisfactory.

(3) The condensation product of aliphatic alcohols having from 8 to 18carbon atoms, in either straight chain or branched chain configuration,with ethylene oxide, e.g., a coconut alcohol-ethylene oxide condensatehaving from 10 to 30 moles of ethylene oxide per mole of coconutalcohol, the coconut alcohol fraction having from 10 to 14 carbon atoms.

(4) Long chain tertiary amine oxides corresponding to the followinggeneral formula, RR'RN- 0, wherein R is an alkyl radical of from about 8to 18 carbon atoms, and R and R" are each methyl or ethyl radicals. Thearrow in the formula is a conventional representation of a semi-polarbond. Examples of amine oxides suitable for use in this inventioninclude dimethyldodecylamine oxide, dirnethyloctylamine oxide,dimethyldecylamine oxide, dimethyltetradecylamine oxide,dimethylhexadecylamine oxide.

(5) Long chain tertiary phosphine oxides corresponding to the followinggeneral formula, RRR"P O wherein R is an alkyl, alkenyl ormonohydroxyalkyl radical ranging from 10 to 18 carbon atoms in chainlength and R and R" are each alkyl or monohydroxyalkyl groups containingfrom 1 to 3 carbon atoms. The arrow in the formula is a conventionalrepresentation of a semi-polar bond. Examples of suitable phosphineoxides are:

Dimethyldodecylphosphine oxide Dimethyltetradecylphosphine oxideEthylmethyltetradecylphosphine oxide Cetyldimethylphosphine oxideDimethylstearylphosphine oxide Cetylethylpropylphosphine oxideDiethyldodecylphosphine oxide Diethyltetradecylphosphine oxideDipropyldodecylphosphine oxide Bis-(hydroxymethyl) dodecylphosphineoxide Bis-(2-hydroxyethyl)dodecylphosphine oxide Z-hydroxypropyl)methyltetradecylphosphine oxide Dimethyloleylphosphine oxide, and

Dimethyl- Z-hydroxydodecyl phosphine oxide.

(c) Ampholytic synthetic detergents: This class of synthetic detergentscan be broadly described as derivatives of aliphatic amines whichcontain a long chain of about 8 to 18 carbon atoms, and an anionicwatersolubilizing group, e.g., carboxy, sulfo, or sulfato. Examples ofcompounds falling within this definition aresodium-3-dodecylaminopropionate and sodium 3dodecylaminopropanesulfonate.

(d) Zwitterionic synthetic detergents: This class of syntheticdetergents can be broadly described as derivatives of aliphaticquaternary ammonium compounds, in which the aliphatic radical may bestraight chain or branched and wherein one of the aliphatic substituentscontains from about 8 to 18 carbon atoms and one contains an anionicwater-solubilizing group, e.g., carboxy, sulfo or sulfato. Examples ofcompounds falling within this definition are 3-(N,N dimethyl Nhexadecylammonio)-propane l sulfonate and3-(N,N-dimethyl-N-hexadecylammonio -2-hydroxypropane-l-sulfonate.

The anionic, nonionic, ampholytic and zwitterionic organic syntheticdetergents mentioned above can be used singly or in combination in thepractice of the present invention. The above examples are merelyspecific illustrations of the numerous detergents which can findapplication within the scope of this invention.

Alkaline builder salts.-Water-soluble inorganic alkaline builder saltswhich can be used alone with the detergent compound or in admixture withother builders are alkali metal carbonates, borates, phosphates,polyphosphates, bicarbonates and silicates. (Ammonium or substitutedammonium salts can also be used.) Specific exsamples of such salts aresodium tripolyphosphate, sodium carbonate, sodium tetraborate, sodiumpyrophosphate, potassium pyrophosphate, sodium bicarbonate, potassiumtripolyphosphate, sodium hexametaphosphate, sodium 13 sesquicarbonate,sodium monoand diorthophosphate, and potassium bicarbonate. Potassiumpyrophosphate finds wide application especially in built liquiddetergent compositions.

Examples of organic alkaline sequestrant builder salts which can be usedalone with the detergent or in admixture with other organic andinorganic builders are alkali metal, ammonium or substituted ammonium,aminopolycarboxylates, e.g., sodium and potassium ethylenediaminetetraacetate, sodium and potassiumN-(2-hydroxyethyl)-ethylenediaminetriacetates, sodium and potassiumnitrilotriacetates and sodium, potassium and triethanolammoniumN-(2-hydroxyethyl)-nitrilodiacetates. Mixed salts of thesepolycarboxylates are also suitable. The alkali metal salts of phyticacid, e.g., sodium phytate are also suitable as organic alkalinesequestrant builder salts (see US. Pat. 2,739,942).

Examples of other suitable organic alkaline sequestrant builder saltsinclude: water-soluble salts of ethane-l-hydroxy-l,l-diphosphonate(e.g., the trisodium and tripotassium salts-see U.S. Pat. 3,159,581);water-soluble salts of methylene diphosphonic acid (e.g., trisodium andtripotassium methylene diphosphonate and the other salts described inUS. Pat. 3,213,030); water-soluble salts of substituted methylenediphosphonic acids (e.g., trisodium and tripotassium ethylidene,isopropylidene, benzylmethylidene, and halomethylidene diphosphonatesand the other substituted methylenediphosphonates disclosed in BritishPat. 1,026,366); water-soluble salts of polycarboxylate polymers andcopolymers as described in the patent of Francis L. Diehl, US. 3,308,067of Mar. 7, 1967 (e.g., polymers of itaconic acid, aconitic acid, maleicacid, mesaconic acid; fumaric acid; methylene malonic acid; andcitraconic acid and copolymers with themselves and other compatiblemonomers such as ethylene); and mixtures thereof.

The detergent softener compositions of this invention can contain any ofthe usual adjuvants, diluents and additives, for example, water, sodiumsulfate, perfumes, antitarnishing agents, antiredeposition agents,bacteriostatic agents, dyes, fluorescers, suds builders, suds depressorsand the like, without detracting from the advantageous properties of thecomposition.

The foregoing synthetic organic detergent softener compositions can beformulated into any of the several commercially desirable compositionforms, for example, granular, flake, liquid and tablet form.

According to another embodiment of this invention, all of the foregoingdescribed softener compounds (Sections A and B) can be employed, aloneor in combination, in novel processes to soften textile material.

(D) PROCESSES OF THIS INVENTION In the practice of this embodiment ofthe present invention, the textile material is treated with a solutionor dispersion of a softener compound, or a mixture of softener compoundsof the invention during either the wash or rinse cycle of the launderingprocess. The detergency builders and synthetic organic detergents usefulin this embodiment are the same as those described above in Section C.The softening compounds which are preferred for use in the followingprocesses are those preferred compounds set out above in Sections A andB.

(1) Process of treating textiles during the wash cycle of the launderingprocess-This embodiment of the present invention relates to a process oftreating textile materials with a solution containing a softeningcompound of the invention. More particularly, this embodiment relates toa process comprising the step of treating said textile materials with anaqueous solution consisting essentially of (a) from 0.001% to about 0.1%of a water-soluble synthetic organic detergent,

- (b) from to about 0.35% of a water-soluble alkaline detergency buildersalt,

(c) from 0.001% to about 0.1% of a softener compound selected from thegroup consisting of subclasses (1)- (3) of the novel softening agentsdescribed above in the Summary section, the previously known compoundsdescribed above in Section B and mixtures thereof, and

(d) the balance being water, all percentages being by weight.

(2) Processes of treating textiles during the rinse cycle of thelaundering pr0cess.This embodiment of the present invention relates to aprocess of treating textile materials during the rinse cycle with thesoftening agents of the present invention. More particularly, thisembodiment relates to a process of treating textiles with an aqueoussolution consisting essentially of (a) from 0.001% to about 0.1% of asoftener compound selected from the group consisting of subclasses (1)-(3) described above in the SUMMARY section and mixtures thereof,

(b) the balance water, all percentages by weight.

(3) Processes of treating textiles during the drying cycle of thelaundering pr0cess.This embodiment of the present invention relates to aprocess of treating textile materials during the drying cycle with thesoftening agents of the present invention. For this embodiment, thesoftener compounds of this invention, including the known compounds ofSection B, are attached to a flexible substrate and used in processessimilar to those of 'U.S. Pat. 3,442,692, i.e., the flexible substratecarrying the fabric softener is placed in a conventional rotary drumclothes dryer together with clothes to be dried, thereby softening theclothes while they are dried and tumbled. It is preferred that thecompositions be prepared according to the teachings of the followingcopending US patent applications: David Russell Morton, Ser. No 788,102,filed Dec. 30, 1968 entitled Textile Softening Agents Impregnated IntoAbsorbent Materials; Howard W. Krueger, Jr., Ser. No. 788,103, filedDec. 30, 1968, entitled Fabric Softening Compositions; and especiallyPablo O. Perez-Zamora, Ser. No. 819,965, filed Apr. 28, 1969, entitledDryer Added Fabric Softening Compositions. As disclosed in theseapplications, preferred softeners for use in this type of compositionand the method of using these compositions to soften clothes in a dryerare the novel zwitterionic compounds disclosed hereinbefore. They arepreferred because they do not stain the fabrics being softened and thecompositions can be used in the washing, rinsing and drying cycles.Particularly preferred are 3(N,N-dimethyl- N eicosylammonio) 2hydroxypropane-l-sulfonate; 3(N,N dimethyl N docosylammonio) 2hydroxypropane-l-sulfonate; and mixtures thereof.

The textile materials which are effectively softened by the treatmentwith the softening compounds of the present invention include artificialfibers and fabrics, either synthetic such as nylons, acrylics andpolyesters, or cellulosic such as cotton, viscose rayon, celluloseacetate, and like materials. It has also been discovered that whennonwoven fabrics such as papers, e.g., tissues, napkins, etc., aretreated with small amounts of the softening agents of this inventionthat they also become softened.

Other compatible softening agents In the practice of all the foregoingembodiments of the present invention other softening agents, as well asadditives such as perfumes, anticorrosion inhibitors and brightenercompounds, can be used in conjunction with the softening compounds ofthe present invention. Examples of other softening agents which can beemployed in combination with the softening agents of this inventionappear in Chwala, Textilhilfsmittel, Vienna .1939, particularly pages'61 to '64; March An Introduction to Tex tile Finishing, London, 1948,particularly Chapter X; and Schwartz-Perry, Surface Active Agents, NewYork, 1949, particularly pages 435-437. Other softening agents which canbe used in conjunction with the softening compounds of the presentinvention are characterized as follows: Ester, etheror amide-likecondensation products containing polyalcohol, polyglycol, polyglycerolradicals and suitable higher molecular, preferably long-chain aliphaticradicals with 12 to 18 carbon atoms, such as for instance fatty acid orfatty alcohol condensation products of the general formula R(C H O),,Hwherein R stands for the monovalent radical of an aliphatic alcohol oran aliphatic acid or amide with 12 to 18 carbon atoms and n for a numberfrom 5 to sulfated or sulfonated longchain aliphatic alcohols;condensation products of longchain fatty acids with hydroxyoramino-sulfonic acids, such as compounds of the formula acylated oralkylated al'kyl polyamines; and quaternary ammonium compounds such asditallowalkyldimethylammonium chloride, cetylpyridinium chloride,cetyltrimethylammonium bromide and tetradecyldimethylbenzylammoniumchloride; and monoor polyesters of longchain fatty acids with monoorpolyoxyarnines.

BRIGHTENER COMPOUNDS Examples of brightener compounds which can be usedin conjunction with the softening agents of the present inventioninclude those disclosed in Stcnsby, Optical Brighteners in FabricSofteners, Soap Chem. Specialties, 41, No. 5, 85-8 (May 1965),Netherlands Pat. 64/08162 (Unilever Jan. 1, 1965), US. Pat. 2,950,253(Boehme Fettchemie -G.m.b.H. Aug. 23, 1960) and Kirk et 3.1., OpticalBrighteners, Encyclopedia Chem. Tech. 3,737- (1964). Specific examplesof brightener compounds are cotton brighteners of thebis-triazinylstilbene type as 4,4'-bis [4-anilino-6-di(hydroxyethyl)amino-sym-triazin- 2-ylamino]-2,2-stilbenedisulfonic acid,

disodium 4,4'-bis(4-anilino-6-morpholino-sym-triazin-2-ylamino)-2,2-stilbenedisulfonate,

disodium 4,4-bis-(4,-6-dianilino-sym-triazin-Z-ylamino)-2,2'-stilbenedisulfonate,

disodium 4,4 bis-(-4-anilino-'6-ethyla-mino-sym-triazin-Z- ylamino-2,2-stilbenedisulfonate and disodium 4,4'bis-(4-anilino '6 N-methylethanolaminosymtriazin-2-ylamino) 2,2'-stilbenedisulfonate;

the bis- N-acylstilbene type such as bis-benzoyl-, bis-paminobenzoyland'bis-dimethoxybenzoylderivatives of 4,4'-diaminostilbene-2,2'-disulfonicacids; the stilbene-triazole type such assodium-4(2H-naphtho[1,2-d]triazol-2- yl)-2-stilbenesulfonate; and thedibenzothiophenedioxide type such as 3,7-bis(pmethoxybenzoylamido)-dibenzothiophene-2,8-disulfonic acid-5,5-dioxide.

Other brightener compounds which can be used are those which areespecially suitable for brightening synthetic fibers. Examples of thesebrighteners include the bis-azoles such as1,2-bis(5-methyl-2-benzoxazolyl)ethylene, bis(S-methyl-Z-benzoxazolyl)thiophene and N-hydroxyethyl 1,2-bis(benzimidazolyl)ethylene; monoazoletypes such as Z-(m-chlorostyryl)-naphtho-[l,2-d]-oxazole and2-styryl-benzoxazole; the pyrazoline type such as 1-p-sulfonamidophenlyl-Zt-p-chlorophenyl-Z-fpyrazoline; and the coumarintype such as 4 methyl-7-dimethylaminocoumarin and3-phenyl-7(diamino-sym-triazinylamino)- coumarin.

When the foregoing brightener compounds are employed in the processes ofthe present invention, it has been found that good results are obtainedwhen the brightener is present in the aqueous solution in the amount ofabout .000l% to about 0.001% by weight of the solution and mostpreferably from about .0002% to about 0.0005 by weight. When saidbrightener compounds are employed in the detergent compositions of theinvention, it has been found that good results are obtained when thebrightener is present in the composition in the amount of from 0.01% toabout 1% and most preferably from about 0.1% to about 0.8% by weight ofthe total composition. Generally, these brightener compounds are used incombination for best brightening results.

The following laboratory procedures were used in connection with theexamples below.

PROCEDURES USED IN EXAMPLES (A) Preparation of test cloths The testcloths are commercial 14" x 14" terry cloth towels (Style 600 fromCannon) which are washed three times with a typical heavy-duty builtanionic detergent (described hereinafter) in a standard automaticwashing machine. After having been washed they are rinsed four times inwater (2 parts water per 1 part of cloth). Thereafter the cloths aredried in a standard automatic dryer. At this point the test cloths areready for use in the tests appearing in the following examples.

(B) Laundering procedures In the tests requiring washing or rinsing ofthe test cloths the following procedures and equipment are used. In allwashing and rinsing operations a one-gallon Dexter washing machine isemployed. The wash cycle in all instances lasts for 10 minutes and isconducted at a temperature of 130 F. The rinsing step is carried out intwo stages; first, the test cloths undergo a pre-rinse which lasts forone minute and then the cloths are given a final rinse which lasts for 2minutes. Both steps are conducted at a temperature of F. The drying stepis carried out in a standard automatic dryer.

The Water used in the laundering process is of 7 grain hardness exceptin the few instances where distilled water is used (these instances arepointed out in the examples). The heavy-duty anionic detergent used inconnection with the washing steps consists essentially of about 17.5% ofa 50/50 mixture of sodium tallow alkyl sulfates and sodiumstraight-chain alkylbenzenesulfonates having an average chain length of13.5 carbon atoms, about 50% sodium tripolyphosphate, about 6% silicate,about 14% sodium sulfate and the balance water.

(C) Determination of softener effectiveness To determine theeffectiveness of the softening compounds of the present invention thefollowing comparisons are made: (1) to demonstrate the effectiveness ofthe softening agents of the present invention when used in conjunctionwith anionic detergents, test cloths (as described in Procedure A) aretreated with the softeners of the present invention in the presence of aheavyduty anionic detergent; and then are compared with separate sets ofsimilar cloths which are treated with a popular cationic softener(described below) added during the rinse cycle; and (2.) to demonstratethe effectiveness of the softening compounds of the present inventionwhen added during the rinse cycle, test cloths (described in ProcedureA) treated during the rinse cycle with the various softening compoundsof this invention are compared with test cloths treated with theforegoing cationic softener.

The comparisons of softening effectiveness between the various softeningagents are made by a panel of three experts. Each expert is presentedwith three pairs (one treated with softening compounds of the presentinvention and the other with the cationic softener) of the treatedCannon terry cloths and asked to handle each pair and select the softerof the two cloths if a difference can be discerned.

The cationic softening agent which is used is a quaternary ammoniumchloride. This quaternary cationic softener has two alkyl groupscontaining 16-18 carbon atoms and is commercially available under thetrade name of Arquad ZIjT-75 and Aliquat H426. This cationic 17 softeneris employed in the following tests during the rinse cycle at a level ofat least 25 parts per million (0.15 g.) which represents the normalusage level.

EXAMPLE I (A) Synthesis of novel compounds (1) 3(N-eicosyl-N,N-dimethylammonio)-2-hydroxypropane 1 sulfonate.-Thefollowing materials are admixed in a two gallon stirred autoclave (apressure vessel with heating means):

Sodium metabisulfite (Na S O )-278 g. (1.39 moles) Methanol (CH OH-128g. (4.0 moles) Sodium hydroxide (NaOH-6 g. (0.15 mole) Water (H O)464 g.

This mixture is heated for a period of 6 minutes while 259 g. or 2.8moles of epichlorohydrin (CH ClCHOCH is added. The resultant temperatureafter the addition of the epichlorohydrin is 200 C. At this point 12 g.of NaOH (0.3 mole) is added and the temperature maintained at 200 C.After waiting another 12 minutes 1045 g. of methanol (32.7 moles) alongwith 800 g. or 2.48 moles of eicosyl dimethylamine (C H N(CH are added.The temperature of the resulting mixture is then increased to 250 C. andthe pressure brought to 50 p.s.i.-g. After allowing the mixture toremain under these condi tions for 45 minutes a sample was taken andanalyzed. It was found that 31% of this mixture was S-(N-eicosyl- N,Ndimethylammonio)-2-hydroxypropane-l-sulfonate. This compound is isolatedby extracting the unreacted materials with petroleum ether and thendried in vacuo.

(2) 3 (N-eicosyl-N,N-dimethylammonio)propane-lsulfonate.-The followingmaterials are admixed in a 5 liter 3-necked flask equipped with amechanical stirrer, condenser and drying tube:

Dimethyleicosylamine325.6 g. (1 mole) Propane sultone122 g. (1 mole) Dry'acetone-2 liters The propane sultone and acetone are addedsimultaneously to the dimethyleicosylamine. This solution is heated andrefluxed for 5 hours. After cooling to room temperature, the precipitatewhich forms is filtered out by a suction filtering device. The filtrateis then added to a 5 liter flask containing 2 liters of dry acetone andrefluxed. During the refluxing, 500 ml. of ethanol is added at whichpoint all of the filtrate is dissolved in the solution. This solution iscooled to 34 C. and left for 12 hours. The precipitate which forms isfiltered out and air dried. It is found to be 86% yield (based on theamine starting material) of 3-(N-eicosyl-N,N-dimethylammonio)-pr0panel-sulfonate.

(3) Eicosyldimethylphosphine oxide-800 ml. of a 3 molar methyl magnesiumchloride in tetrahydrofuran solution (contains 2.4 moles methylmagnesium chloride) is placed in a 3 liter 3-necked glass flask. Theflask is equipped with a methanical stirring condenser, dropping funnel,thermometer, nitrogen inlet, and an outlet through a drying tubecontaining Drierite. To this solution, 110 g. (0.8 mole) of diethylhydrogen phosphite is added drop- Wise, while maintaining thetemperature at 25 C. using an ice bath. After addition of the phosphitethe ice bath is removed and the solution stirred one-half hour. In aseparate flask 320 g. or 0.88 mole of eicosyl bromide is melted anddissolved in 100 ml. of dry tetrahydrofuran. The temperature of thereaction is raised to 40 C. The eicosyl bromide solution is then addeddropwise to the fore going mixture. The resulting mixture is stirred andrefluxed for 18 hours. Thereafter the solution is cooled to 30-35 C. andpoured into a beaker containing 180 ml. of water, 1200 ml. of ice and220 ml. of concentrated HCl and; then, immediately poured into aseparator funnel where the layers are separated by extracting the waterlayer with 200 ml. of diethylether. The remaining solvents areevaporated on a flask evaporator and the residue dissolved in 600 ml. ofCHCl This solution is washed with 220 ml. of 10% HCl and then with ml.of 15% Na CO The solution is dried and the MgSO filtered from thefiltrate on a flash evaporator. The residue is distilled through alarge-bore, short-path condenser to produce 0.4 g. of (30%)eicosyldimethylphosphine oxide.

(4) Ethoxylated alcohol compounds-600 g. or 2.0 moles of eicosyl alcoholare admixed with 0.8 g. of sodium hydroxide (anhydrous pellets) in a twogallon stirred autoclave and the temperature of the mixture increased toabout 300 C. 265 g. or 6.0 moles of ethylene oxide (liquid form) is thenadded to the mixture over a period of about 10 minutes with thetemperature maintained at about 300 C. The reaction mixture is thencooled to a temperature below 150 C. and the pressure is vented to 40psig The product is then removed by blowing it out of the autoclavevessel. The product is essentially free from impurities, and is found tohave a molecular weight of 430. This is determined by hydroxyl valueanalysis (titrating with a 0.1 N potassium hydroxide solution).

By replacing the amount of ethylene oxide in the foregoing reaction witheither 880 g. (20 moles) or 1760 g. (40 moles) of ethylene oxide, it isfound that the resulting products have excellent softeningcharacteristics.

Also, the 600 g. or 2.0 moles of eicosyl alcohol in the foregoingreaction could equally be replaced with 2.0 moles of heneicosyl alcohol,tricosyl alcohol, tetracosyl alcohol, pentacosyl alcohol, or hexacosylalcohol to produce reaction products which have excellent softeningcharacteristics.

(5) Sulfated ethoxylated alcohol compounds.-300 grams (or 0.87 mole) ofthe condensation product of reacting one mole of eicosyl alcohol withone mole of ethylene oxide [as shown in the preceding synthesis (4)] isreacted with 106 g. or 0.9 mole of chlorosulfonic acid in a 500 ml.glass beaker having an agitator connected thereto. This reaction takesplace at 150 to C. After about 5 minutes the mixture is added to a 1500ml. glass beaker containing 875 g. of water and 25 g. of sodiumchloride. To this solution, 50 g. of a 50% sodium hydroxide solution isadded. By analysis the resulting product has a molecular weight of 415which is found by analytically determining the SO; content of theproduct (titrating with hexadecyltrimethylammonium bromide).

(6) Sodium-Z-acetoxydocosyl-1-sulfonate.-324.5 g. of 1.0 mole ofdocosanyl-l-oxide is mixed in a 5 liter glass flask with 104.0 g. or 1.0mole of sodium bisulfite and 2.0 liters of a 50% solution ofisopropanol. This mixture is refluxed for 1 week in a steam bath 100 C.The mixture is then cooled to room temperature and the precipitatefiltered out using a Buckner suction funnel. The precipitate is washed 3times with pentane and then dried in vacuo. The resultant product is a75% yield of sodium-Z-hydroxydocosyl-l-sulfonate, based on the epoxidestarting material. In a separate 5 liter glass flask 380.5 g. or 3.73moles of acetic anhydride and 1592 g. or 20.15 moles of pyridine aremixed and stirred with an electric stirring device for a period of 30minutes. To this mixture 428.6 g. or 1 mole of the foregoing reactionproduct (sodium-Z-hydroxydocosyl-l-sulfonate) is added. This mixture isthen heated to a temperature of 4550 C. on an electric heating mantlefor 12 hours. The temperature is then raised to 100-105 C. and themixture refluxed for 10 days. At the end of the 10-day period themixture is poured into glass beakers and the solvents evaporated on asteam bath (100 C.). The solid residue is dissolved in 3800 m1. ofdioxane containing about 5 g. of charcoal and the solution warmed in asteam bath for 12 hours. The solution is filtered out and the filtratecooled to room temperature. The precipitate is filtered out and dried invacuo. The resultant material represented a 50% yield of sodium-2-acetoxydocosyl-l-sulfonate based on the hydroxysulfonate startingmaterial.

19 EXAMPLE 11 To illustrate the surprising increase in softeningeffectiveness between the softening compounds of the present inventionand their lower homologs the following tests are conducted.

Test cloths treated in accordance with procedure A are exposed tosolutions of known concentrations of the softening compounds of thisinvention having an alkyl radical containing 20 carbon atoms, and theircorrespond ing lower homologs having alkyl radicals containing either 16or 18 carbon atoms respectively. Such treatments are carried out duringa normal rinse cycle using procedure B. After drying the test cloths,they are compared using procedure C for softness. The results of thiscomparison are shown in the following table.

No. of carhens in long alkyl carbon chain Percent of compound by weightof solution Soft- Compound ness (A) Lower homologs:

3-(N-hexadecyl-N,N-dimethylammonio)-2- hydroxypropane-l-sulfcnate.

3-(N-hexadecyl-N,N dimethylamm onio)-2-hydroxypropane l-sulfonate.

Hexadecyldimethylphosphine oxide.

Reaction product of reacting 1 mole of hexadeeyl alcohol with 3 moles ofethylene oxide.

Sulfated reaction product of reacting 1 mole of hexadecyl alcohol with 1mole of et1ylene oxide (sodium a 16 0. 1 Fair.

20 0. 015 Good.

salt) Sodium-2-acetoxydocosyl-l- 20 0. 015 D0.

sulfonate.

It can be seen that it requires twice as much of the compound having analkyl radical of 16 carbon atoms (0.1%) to achieve the same degree ofsoftening as achieved by the compound (higher homolog) having an alkylradical of 18 carbon atoms (0.05% However, even more surprising is theobservation that using over three times as much of compound having analkyl radical of 18 carbon atoms (0.05%) does not soften cloths to thesoftness obtained using the softening compounds of this invention whichhave an alkyl radical of 20 carbon atoms (0.015%). No reason is knownfor this unexpected increase in softening effectiveness between the Cand C homologs. This observation is particularly surprising in view ofthe fact that there is a diiference in molecular structure of only 2methylene groups between the C and C compounds.

EXAMPLE III The following tests are made to illustrate the surprisingsoftening effectiveness of the softening compounds of the presentinvention when added during the wash cycle. Four separate wash cyclesper softening compound are performed according to procedure 'l3, eachwash cycle containing 6 g. of the heavy-duty built anionic detergent(described previously), and respectively. 0.075 g., 0.15 g., 0.3 g. and0.6 g. of each of the following softening compounds:

3- (-N-eicosyl-N,N-dimethylammonio -2-hydroxypropanel -sulfonate3-(N-eicosyl-N,N-dirnethylammonio)propane-1- sulfonateEicosyldimethylphosphine oxide Reaction product of 1 mole of eicosylalcohol with 3 moles of ethylene oxide Sulfated reaction product of 1mole of eicosyl alcohol with 1 mole of ethylene oxide (sodium salt)Sodium 2-acetoxydocosyl-l-sulfonate Eicosyldimethylamine oxide The washload of each cycle contains a cloth load of 5% by weight of test clothstreated according to procedure A. After washing the test cloths, eachset is rinsed and dried using standard techniques. It is observed thatall the dried test cloths are softened to an equal degree. To a separateset of test cloths treated in accordance with procedure A comprising a5% by weight cloth load in a rinse cycle, 0.15 g. of the cationicsoftener described in procedure C is added. These cloths aresubsequently dried and compared to the towels treated with the foregoingsoftening compounds. .It is found that the softness or hand of all thecompared cloths is substantially equal and that no degree of differencein softness is discernible.

Results similar to the foregoing are obtained in that cloths similarlytreated are softened if the above described softening agents arereplaced by any of the specific softening compounds found above atSection A(1)(a) preferred zwitterionic compound." Section A(2)(a)preferred tertiary phosphine oxide compounds; Section :B(1) (a)preferred ethoxylated alcohol compounds. Section B(3)(a) preferredethoxylated alcohol sulfate compounds"; Section A(3)(a) preferredanionic sulfonate compounds; and Section B(l)(a) preferred tertiaryamine oxide compounds."

EXAMPLE IV The following test illustrates the softening effectiveness ofthe softening compounds of this invention when employed in the rinsecycle. Test cloths treated according to procedure A (each test loadcontaining a cloth load of 5% by weight) are washed for 10 minutes in anaqueous solution containing 6 g. of the heavy-duty anionic detergentdescribed in procedure B. After the washing step the cloths are eitherrinsed in an aqueous solution containing 0.15 g. of the cationicsoftener described in procedure C for 0.15 g. of one of the followingsoftening compounds:

3-(N-eicosyl-N,N-dimethylammonio)-2-hydroxypropane-l-sulfonate3-(N-eicosyl-N,N-dimethylammonio) -propane-1- sulfonateEicosyldirnethylphosphine oxide Reaction product of reacting 1 mole ofeicosyl alcohol with 3 moles of ethylene oxide Sulfated reaction productof reacting 1 mole of eicosyl alcohol with 1 mole of ethylene oxide(sodium salt) Sodium Z-acetoxydocosyl-l-sulfonate After drying all testcloths treated with the softening compounds of this invention arecompared with the cloth treated with the cationic softener usingprocedure C. It is found that those test cloths treated with theforegoing softening agents are substantially softer than those treatedwith the cationic softener.

Similar results can be obtained in that cloths similarly treated aresoftened by replacing the foregoing softening agent with any of thespecific softening compounds found at Section A(1)(a) preferredzwitterionic compound. Section A(2)(a) preferred tertiary phosphineoxide compounds; Section B(2)(a) preferred ethoxylated alcoholcompounds. Section B(3)(a) preferred ethoxylated alcohol sulfatecompounds; and Section A(3) (a) preferred anionic sulfonate compounds.

EXAMPLE V This example shows that the brightening efiiciency of atypical cotton brightener in a softening composition is much better whenthe softening agents of the present invention are used as the softeningcompounds in a softener/brightener formulation than when a typicalcationic compound is used. In this test, test cloths described inprocedure A are treated with aqueous dispersions consisting of about0.005% by weight of one of the softening agents found in the followingtable and about 0.0002% by Weight of a bis-triazinylstil'bene typecotton brightener [4,4' bis-(4-anilino-6-di[hydroxyethyl]amino symtriazin-Z-ylamino)-2,2'-stilbenesulfonic acid]. To each solution(dispersion) a set of test cloths is added in sufiicient amount to reacha cloth load of 5% by Weight. After ten minutes exposure time, followedby rinsing in distilled water and drying, the test cloths are placed ina fiuorimeter to determine the extent of fluorescence conferred to thefabric. The following results are obtained:

Fluorimeter Formulation: reading A -50 mixture of the reaction productsof reacting one mole of eicosyl alcohol and one mole of docosyl alcoholwith 10 moles of ethylene oxide The above described cationicsoftener-i-the above brightener When no softener is added to thebrightener solution 101 Thus, the interference with brightening by thesoftening agents of the present invention is very slight while theinterference given by the cationic softener is very extensive.

Excellent softening with no interference with brightening is obtainedwhen any of the above listed softening agents are replaced by any of thesoftening compounds found at Section A(1)(a) preferred zwitterioniccompound. Section A(2)(a) preferred tertiary phosphine oxide compounds;Section 13(2) (a) preferred ethoxylated alcohol compounds. SectionB(3)(a) preferred ethoxylated alcohol sulfate compounds; Section A(3)(a) preferred anionic sulfonate compounds; and Section 13(1) (a)preferred tertiary amine oxide compounds.

Results similar to those above are observed when the brightener used inthe foregoing test is replaced with any of the brighteners found atSummary 'D(2) Brightener Compounds.

COMPOSITIONS The softening compounds of the present invention can bebeneficially employed in granular detergent compositions containingbrighteners.

The following table sets forth examples of such formulations. Theseformulations are found to have excellent detergency and brightening asWell as excellent softening characteristics.

TABLE I Component 1 2 (a) Softening agent:

3-(N-eicosyl-N,N-dimethylammonio)-2-hydroxypropane-l-sulionate3-(N-docosyl-N,N-dimethylammonio)-2-hydroxypropane-l-snlionate3-(N-eicosyl-N,N-dimethylammonio)-propane-1- su1ionateEicosyldimethylphosphine oxide Docosyldimethylphosphine oxide Eicosylalcohol ethylene oxide (3 moles) reaction product Eicosyl alcoholethylene oxide (5 moles) reaction product Suliated reaction product of 1mole ethylene oxide and 1 mole eicosyl alcohol (sodium salt)Eicosyldirnethylamine oxide Sodium 2-acetoxydocosyl sulfonate Buildermaterial: Sodium tripolyphosphate. Potassium ethane-l-hydro Sodiumnitrilotriacetate Sodium ethane-l-hydroxy-l,l-diphosphona (c) Detergent:

Sodium straight chain alkyl (Av. One) benzene sulionate Sodium tallowalkyl sulfateS-(N,N-dimethyl-N-tallow-alkylammonio)-2-hydroxypropaue-l-sulionate 5 5Reaction product of S03 and C alpha-olefin neutralized with NaOH Tallowalcohol ethylene oxide (5 moles) reaction product Tallow alkyldimethylphosphine oxide Tallow alkyl di 2-hydroxy ethyl)-amine oxide ((1)Brigbtener:

[4,4-bis(4-anilino-6-dihydroxyethylamino-sym- Examples (percent byweight of the composition) iazin-Z-ylemino)-2,2-stilbenedisulf0nic acid]0. 15 0. l6 0. 17 0. 16 0. l6 0. 16 0. 16 0. 17 0. 16

4,4-bis(4-anilino-o-dimorpholinosym-triMin-2- ylamino)-2,2-stilbenedisulfonate 0.14 0. 16 0. 13 0. 15 0. 16 0. 16 0. 16 0. 1 0. 16 1Disodium 4,4-bis(4,6-dianilino-sym-triazin-2- 3 0 7y1amino)-2,2-stilbene disulionate 0.14 0. 14 0. 14 0.16

(e) Miscellaneous:

Sodium silicate (S10 zlNazo =1.6) 6 5 6 6 5 6 6 Benzotriazo1c .02 .02.02 .02 Sodium pcrborate 5 5 5 5 Sodium sulfate 10 13 5 7 12 13 Coconutammonia amide 2 2 2 Sodium carboxymethyl cellulose 1 6 1. 6 1. 6 1. 2 11 6 1. 6 1. 6 1. 6 1. 6 Sodium random octadecyl phosphonate 0 2 0.3 0.10.2 0 2 0.3 0. 1 0.3

Water Form Granular 23 The softening compounds of the present inventioncan the rollers and, after solidifying (or substantially slidifyalso beemployed beneficially in homogeneous liquid foring) the treatedsubstrate, provides a substrate having its mulations comprised of either(1) softening agents, synfibers substantially completely coated and itsfree space thetic detergents, brightening agents and water, or (2)substantially completely filled and having about 2 grams softeningagents, brightener and water. Liquid formula- 5 of Carbowax 1540 per 100square inches of the substrate.

tion (1) is found to have excellent detergency and bright- Thesubstrate, containing the solidified substrate coating, ening as well assoftening characteristics. Liquid formulais then passed through a pairof transfer rollers which tion (2) is found to have excellent softeningand brightconsists essentially of a pair of hard rubber rollers, theening characteristics. The latter formulation can be embottom rollersitting in a trough which contains the liquiployed beneficially aseither a Wash or rinse additive. Exfied outer coating which is aformulation (M.P. 155 F.) amples of these liquid formulations are setforth in the consisting of:

following table.

TABLE 11 Examples (percent by weight of the composition) Component l8 1920 21 22 23 24 25 26 27 2s 29 30 (a) Softening a cut:

3-(Nieicosy -N, N-dimethyl ammonio)-2-hydroxy propane-l-suliona eElcosyldimethylphosphlne oxide l0 Docosyldimethylphosphine oxi Eicosylalcohol ethylene oxide (2 moles) reaction product. Docosyl alcoholethylene oxide (20 moles) reaction product 5 Sulfated reaction productof 3 moles ethylene oxide and 1 mole eicosyl alcohol (sodium salt)Eicosyldimethylaruiue oxide. 5 10 Sodium 2-acetoxyeicosyl sulfcnate. (b)Builder material: Sodium nitrilotriacetat (c) Detergent: Ammoniumstraight chain alkyl (Avg. 013.5) benzene Sulfonste 2. 5 2. 5 2. 5 2. 52.5 (d) Brightener:

[4, 4-bis (4-anilino-6-dihydroxyethylamino sym-triazin-2-ylamino)-2,2-stilbenedisulfonicacid] 0.17 0.26 0.24 0.01 0.07 0.13 0.07 0.07 0.134,4-bis (4-anilino-6-dimorpholino-sym-triazin-2-ylamino)2 2'-stil beuedisult'onate 0.07 0.04 0.34 0.13 0.07 0.06 0.07 0.07 Dlsodium 4,4'-bis'anilino-sym-tria benedisullonate n. 0.07 0.06 0.08 0.07 0.07 (e)Miscellaneous:

Balance Liquid Percent EXAMPLE v1 3 [N,N dimethyl-N-alkyl(C -C)ammonio]-2 A non-woven cloth substrate, Stock A, is wrapped about gg ii g g g L f ggg 60 a hollow, tubular cardboard core, and a rod is passedStat a 18 g 15 through the core and held so as to allow the substrate toISO r0 {A X6 23 5 easily unroll. More particularly, Stock A is adry-laid, 40 g g nonwoven cloth comprising about 70% regeneratedcellulose (American Viscose Corporation) and about 30% hy- As thetreated substrate passes through the turning drophobic binder-resins(Rhoplex HA8 on one side of rollers, the outer coating formulationadheres to the the cloth, Rhoplex HA-16 on the other; Rohm & Haas,bottom roller and is brought into contact with the face- Inc.). Thecloth has a thickness of about 4 to 5 mills, a down side of the passingsubstrate, thereby achieving a basis weight of about 26 grams per squareyard, and fabric softening composition having an outer coating on weighsabout 2 grams per 100 square inches. The fibers only one of its sides.After solidifying, the opposite side are about 4 inch in length, about1.5 denier and are of substrate is then passed face-down through asecond oriented substantially haphazardly. The fibers were lubpair oftransfer rollers and solidified to achieve a fabric ricated with sodiumoleate. softening composition having an outer coating on both A nonionicsubstrate coating, having a melting point Sldesof about 114 R, isprepared by melting 200 grams of This latter composition issubstantially solid, stable to substantially solid, waxy, polymer ofethylene glycol (Cardecomposition, not runny or dripping, and which,bowax 1540; M1. about 114 F.) in a container set into although waxy tothe touch, does not cause the composiawater bath heated to 150 F. tostick together when folded. The fabric softening com- The substratecoating is applied to the substrate by position has an outer coating ofabout 6 grams per 100 means of a padding machine. This machine, AtlasLabosquare inches of substrate. The total amount of inner ratory Wringer(Model No. LW-391, Type llW-l) and outer coatings is about 8 grams per100 square inches made by Atlas Electrical Devices Company, Chicago,111., of substrate, and results in a Weight ratio of 4:1 by weight iscommercially available and is especially adaptable to of the substrate.small scale use. The machine basically comprises two hard Prior torerolling, the fabric softening composition can rubber rollers mountedso that their surfaces touch (fit be perforated at desired uniformlengths, or instead of flush together). Pressure can be exerted onto therollers g, the Composition can be Cut a 'fid l ngths and adjusted bymeans of weights. A trough-like pan unand packaged as individual sheets.der the rollers is so constructed as to provide guiding A 12inch by 8 /3inch sheet of this composition is tested members along its length forfeeding or leading the subfor softening performance in an automaticKenmore strate into the rollers. The liquidified substrate coating iselectriC Clothes y Satisfactory fabric Softening then placed into thepan, and the pan is heated to about and fabric softener release areachieved and there is no 150 F. to keep the substrate coating in aliquid state. The tai g f the fabrics, Which are left With a pleasantsubstrate is unrolled and passed submersed through the perfume odor andno static cling.

substrate coating in the pan. The substrate, traveling at a A similarfabric softening composition is obtained rate of 5 to 6 feet per minute,is then directed upward and when dimethylditallowalkylanunonium chlorideis subthrough the turning rollers onto which no weights are exstitutedfor the outer coating formulation used above and erted and whichsqueezes off excess substrate coating. The results in a fabric softeningcomposition having an outer turning rollers continuously pull thesubstrate through coating with a melting point of about F.

Compositions with similar softening effectiveness result if any of theforegoing softener compounds are replaced with any of the specificcompounds found at Section A(1)(a) preferred zwitterionic compound.Section A(2) (8.) preferred tertiary phosphine oxide compounds; SectionB(2) (a) preferred ethoxylated alcohol compounds; Section B(3) (a)preferred ethoxylated alcohol sulfate compounds; Section A(3)(a)preferred anionic sulfonate compounds; and Section B(1)(a) preferredtertiary amine oxide compounds.

Compositions with similar brightening effectiveness result if any of theforegoing brightening compounds are replaced with any of the specificbrighteners found at Summary D(2) Brightener Compounds.

The foregoing description and examples of this invention have beenpresented describing certain operable and preferred embodiments. It isnot intended that the invention should be so limited since variationsand modifications thereof will be obvious to those skilled in the art,all of which are within the spirit and scope of the invention.

What is claimed is:

1. A detergent composition with softening properties consistingessentially of:

(a) from about 1% to about 20% of a water-soluble synthetic organicdetergent selected from the group consisting of anionic detergents,nonionic detergents, ampholytic detergents and zwitterionic detergents,said detergents having one long alkyl group containing less than 20carbon atoms,

(b) from to about 90% of Water-soluble alkaline detergency buildersalts,

(c) from about 1% to about 25% of a softening agent having the formulawherein M is selected from a group consisting of alkali metal, ammoniumand substituted ammonium cations, and R is an alkyl group containingfrom 20 to 30 carbon atoms; and (d) the balance being water, allpercentages by weight. 2. The detergent composition of claim 1 whereinthe amount of softening agent (c) present is from about 2.1% to about 3.The detergent composition of claim 1 wherein the softening agent (c) isan anionic sulfonate compound of the formula wherein M is selected fromthe group consisting of alkali metal, ammonium and substituted-ammoniumand where R is an alkyl group containing from to 26 carbon atoms.

4. A detergent composition with softening properties consistingessentially of:

(a) from 1% to of a softening agent having the formula O(J=O CHR$CH2SOaM wherein M is selected from a group consisting of alkali metal,ammonium and substituted ammonium cation, and R is an alkyl groupcontaining from 20 to 30 carbon atoms;

20 (b) from about 1% to about of a water-soluble alkaline detergencybuilder salt, and

(c) the balance being water, all percentages by weight,

5. The detergent composition of claim 4 wherein the amount of softeningagent (a) present is in the amount of from about 10% to about 20%.

6. The detergent composition of claim 4 wherein the softening agent (a)is an anionic sulfonate compound of the formula wherein R is an alkylgroup containing from 20 to 26 carbon atoms.

f7. A liquid softener composition consisting essentially o (a) fromabout 1% to about 25 of a softening agent having the formula o-o==o R- ICH2SO:M

wherein M is selected from a group consisting of alkali metal, ammoniumand substituted ammonium cations, and R is an alkyl group containingfrom 20 to 30 carbon atoms; (b) from about 0.01% to about 1% of abrightener compound, and (c) the balance being water, all percentages byweight. 8. The liquid softener composition of claim 7 wherein the amountof softening agent (a) is present in the amount of from 1% to about 10%and the brightener compound (()b8) 7is present in the amount of about0.1% to about 9. The liquid softener composition of claim 7 wherein thesoftening agent (a) is an anionic sulfonate com pound of the formulawherein R is an alkyl group containing from 20' to 26 carbon atoms.

10. The process of simultaneously washing and softening textilematerials comprising the step of treating said textile materials bycontacting them with an aqueous solution consisting essentially of (a)from 0.001% to about 0.1% of a water-soluble synthetic organic detergentselected from the group consisting of anionic detergents, nonionicdetergents, ampholytic detergents and zwitterionic detergents, saiddetergents having one long alkyl group containing less than 20 carbonatoms,

(b) from 0% to about 0.35% of a water-soluble alkaline detergencybuilder salt,

(c) from 0.001% to about 0.1% of a softening agent having the formulawherein M is selected from a group consisting of alkali metal, ammoniumand substituted ammonium cations, and R is an alkyl group containingfrom 20 to 30 carbon atoms; and

(d) the balance water, all percentages by weight.

11. The process of claim wherein the aqueous solution contains fromabout 0.002% to about 0.01% softening agent.

12. The process of claim 10 wherein the softening agent is an anionicsulfonate compound of the formula wherein M is selected from the groupconsisting of alkali metal, ammonium and substituted ammonium andwherein R is an alkyl group containing from to 26 carbon atoms.

13. The process of claim 10 wherein the aqueous solution also containsfrom about 0.0001% to about 0.001% by weight of a brightening agentselected from the group consisting of 4,4-bis- [4-anilino-6-di(hydroxyethyl) amino-sym-triazin- 2-ylamino]-2,2'-stilbenedisulfonicacid,

disodium 4,4bis(4-anilino-6-morpholino-sym-triazin-Z- ylamino2,2-stilbenedisulfonate,

disodium 4,4'-bis(4,6-dianilino-sym-triazin-2-y1amino)-2,2-stilbenedisulfonate,

disodiurn 4,4-bis 4-anilino-6ethylamino-sym-triazin-Z- ylamino)-2,2-stilbenedisulfonate,

disodium4,4'-bis(4-anilino-6-methylethanolamino-symtriazin-Z-ylamino)2,2'-stilbenedisulfonate,

sodium-4(2H-naphtho 1,2-d] triazol-2-yl -2- stilbenesulfonate,

2-(m-chlorostyryl)-naphth-[1,2-d1oxazole,l-p-sultonamidophenyl-3-p-chlorophenyl-2-pyrazoline,and

1,2-bis(S-methyl-Z-benzoxazolyl)ethylene, and mixtures thereof.

14. The process of softening textile materials comprising the step oftreating said textile materials by contacting them with an aqueoussolution consisting essentially of (a) from 0.001% to about 0.1% of asoftener compound having the formula wherein M is selected from a groupconsisting of alkali metal, ammonium and substituted ammonium cations,and R is an alkyl group containing from 20 to carbon atoms; and (b) thebalance being water, all percentages by weight. 15. The process of claim14 wherein the aqueous solution contains from about 0.002% to about0.01% softening agent.

16. The process of claim 14 wherein the softening agent is an anionicsulfonate compound of the formula wherein M is selected from the groupconsisting of alkali metal, ammonium and substituted ammonium and wherein R is an alkyl group containing from 20 to 26 carbon atoms.

17. The process of claim 14 wherein the aqueous solution also containsfrom about 0.0001% to about 0.001% by weight of a brightening agentselected from the group consisting of 4,4'-bis- 4-anilino-6-di(hydroxyethyl amino-sym-triazin- 2-ylamino]-2,2'stilbenedisulfonic acid,disodium 4,4'-bis(4-anilino-6-morpholino-sym-triazin-2- ylamino-2,2'-stilbenedisulfonate,

disodium 4,4-bis(4,-dianilino-sym-triazin-2-ylamino)-2,2'-stilbenedisulfonate,

disodium 4,4'-bis(4-anilino-6-ethylamino-sym-triazin-2- ylamino-2,2-stilbenedisulfonate,

disodium 4,4-bis(4-anilino-6-methylethanolamino-symtriazin-Z-ylarnino)-2,2'-stilbenedisulfonate,

sodium-4 2I-I-naphtho[ 1,2-d1 triazol-Z-yl) -2- stilbenesulfonate,

2- m-chlorostyryl) naphth-[ 1,2-d1-oxazole,

1-p-sulfonamidophenyl-3-p-chlorophenyl-2-pyrazoline,

and

1,2-bis(5-methyl-2-benzoxazolyl)ethylene, and mixtures thereof.

References Cited UNITED STATES PATENTS 2,061,617 11/1936 Downing et a12528.7 X 2,061,618 11/1936 Downing et a1 2528.7 X 2,061,619 11/1936Downing et al. 252353 X 2,061,620 11/1936 Downing et al. 252353 X2,086,215 7/1937 De Groote 260513 R 2,094,451 9/1937 Guenther et al.260-458 X 3,332,880 7/1967 Kessler et al. 252161 3,014,042 12/1961 Mantz260-309.7 3,296,145 1/1967 Findlan et al. 2528.8 X 3,318,817 5/1967Smith 252152 3,329,609 7/1967 Blomfield 2528.75 X 3,351,557 11/1967Almstead et al. 252152 X 3,400,148 9/1968 Quimby 252152 X 3,454,4947/1969 Clark et al. 2528.8

OTHER REFERENCES Iungermann et al., Fatty Amine Oxides, Soap andChemical Specialties, September 1964, pp. 59-62.

LEON D. ROSDOL, Primary Examiner H. A. PIT LICK, Assistant Examiner US.Cl. X.R.

@2 3 TED STATES PATENT. @FFKCE QETEFPCATE OF CQRECTN- Patent N 9, 569Dated March 14, 1972 Inventofls) Charles Bruce McCarty It is certifiedthat error appears in the above-identified patent and that said LettersPatent are hereby corrected as shown below:

Column 15, line 32, (Unilever Jan. 1, 1965) should be (Unilever Jane 18,1965) Column 15, line 36, after "type" insert such Column 17, line 59,"methanical should be mechanical Columns 21 and 22, Table I, "5" and 3"adjacent "Tallow alcohol ethylene oxide (5 moles) reaction product"under Examples 3 and 4, respectively, should be under Examples 2 and 3,

respectively.

Columns 21 and 22, Table I, "5" adjacent "Tallow alkyldimethyl phosphineoxide" and under Example 5 should be under Example 4. Column 24, line 1,"slidifying" should be solidifying Column 24, line 48, before"substrate" insert the Column 26, line 3, Claim 4, after "weight deleteand insert Signed and sealed this 7th day of November 1972.

(SEAL) Attest 2 EDWARI MQFLETCHER ,JRa ROBERT GOTTSCHALK AttestingOfficer Commissioner of Patents

